CN114846032A - Radical polymerizable resin composition and cured product thereof - Google Patents

Radical polymerizable resin composition and cured product thereof Download PDF

Info

Publication number
CN114846032A
CN114846032A CN202080089185.1A CN202080089185A CN114846032A CN 114846032 A CN114846032 A CN 114846032A CN 202080089185 A CN202080089185 A CN 202080089185A CN 114846032 A CN114846032 A CN 114846032A
Authority
CN
China
Prior art keywords
resin composition
radical polymerizable
acid
mass
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080089185.1A
Other languages
Chinese (zh)
Inventor
坂口阳一郎
齐藤广平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of CN114846032A publication Critical patent/CN114846032A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0478—Copolymers from unsaturated polyesters and low molecular monomers characterised by the monomers used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention can provide a radical polymerizable resin composition which can suppress shrinkage while maintaining strength by adding an appropriate amount of an expanding material to a radical polymerizable resin composition which undergoes curing shrinkage due to a decrease in free volume of a liquid component during curing. The radical polymerizable resin composition of the present invention contains a radical polymerizable compound (a), an expanding material (B), a radical polymerization initiator (C), and an aggregate (D). The aggregate (D) comprises cement. The aggregate (D) is 330 to 800 parts by mass per 100 parts by mass of the radically polymerizable compound (A).

Description

Radical polymerizable resin composition and cured product thereof
Technical Field
The present invention relates to a radical polymerizable resin composition and a cured product thereof.
The present application claims priority based on Japanese application No. 2019-235911, 12/26/2019, the contents of which are incorporated herein by reference.
Background
When a vinyl monomer in a liquid state is used for polymerization, considerable shrinkage occurs. Due to this shrinkage, strain problems arise in the case of using vinyl monomers for industrial products. Therefore, it is industrially very useful to prepare a resin having a small shrinkage rate during polymerization.
A radical polymerizable resin composition represented by an unsaturated polyester resin, a vinyl ester resin (epoxy acrylate) or the like generally undergoes shrinkage during curing. Since "styrene" and "methyl methacrylate" as monomers shown in table 1 of non-patent document 1 are often used as monomers, an unsaturated polyester resin in ordinary compounding is accompanied by volume shrinkage of about 8 to 12%, and a vinyl ester resin is accompanied by volume shrinkage of about 8 to 10%.
This value is considerably larger than the volume shrinkage of 3 to 6% in a conventional epoxy resin. Therefore, the application of the unsaturated polyester resin or vinyl ester resin to industrial applications or the expansion of the unsaturated polyester resin or vinyl ester resin to various industries and applications other than the above is hindered.
As a method for solving this problem, patent document 1 suggests that the use of polystyrene beads as a low shrinkage material can reduce the number of production steps and the production time, and that a low shrinkage unsaturated polyester resin composition having excellent low shrinkage, dimensional stability and surface smoothness can be produced.
Further, patent document 2 suggests that by blending an a-B type block copolymer into an unsaturated polyester resin composition, a low shrinkage unsaturated polyester resin composition which has low shrinkage during curing and can produce a molded article having excellent heat resistance can be obtained.
Further, patent document 3 suggests that a low shrinkage unsaturated polyester resin composition having a large low shrinkage effect at the time of molding at normal or medium temperature and high water resistance can be obtained by mixing an a-B type block copolymer (vinyl acetate-styrene type) composed of segments of a and B with fine particle silicic acid with an unsaturated polyester resin.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-315198
Patent document 2: japanese patent No. 2794802
Patent document 3: japanese laid-open patent publication No. H05-222282
Non-patent literature
Non-patent document 1: long rattan stiffness, overlapping body は cannot avoid か (whether volume shrinkage during aggregation is unavoidable), and the polymer 27, vol 2 month (1978), pages 108 to 111.
Disclosure of Invention
Problems to be solved by the invention
In conventional radical polymerizable resin compositions, in order to produce a resin having a low shrinkage, a thermoplastic resin such as polystyrene is blended alone or 2 or more kinds of block copolymers are used. They function mostly as "shrink-resistant materials".
Further, these resin compositions are limited in many applications to applications in which heat molding is performed at a temperature of not less than a middle temperature range, such as Sheet Molding Compounds (SMC) and Bulk Molding Compounds (BMC), in view of the concept of offsetting the thermal expansion of the thermoplastic resin due to heat generation during curing from the curing shrinkage of the unsaturated polyester resin.
The present invention has been made in view of the above-mentioned conventional circumstances, and an object thereof is to provide a radical polymerizable resin composition having a small shrinkage rate, which is not limited to a molding method, a use temperature, an application, and the like, because the entire resin composition expands at a certain rate during curing and is then stable, by introducing an expansion material instead of a shrinkage prevention material.
Further, an object of the present invention is to provide a cured product of a radical polymerizable composition which does not deteriorate flowability.
Means for solving the problems
That is, the present invention is represented by the following [1] to [8 ].
[1] A radically polymerizable resin composition comprising a radically polymerizable compound (A), an expandable material (B), a radically polymerizable initiator (C), and an aggregate (D), wherein the aggregate (D) comprises cement,
the aggregate (D) is 330 to 800 parts by mass per 100 parts by mass of the radically polymerizable compound (A).
[2] The radically polymerizable resin composition according to [1], wherein the radically polymerizable compound (A) comprises a vinyl ester resin and a radically polymerizable unsaturated monomer.
[3] The radical polymerizable resin composition according to [1] or [2], wherein the swelling material (B) contains at least 1 material selected from the group consisting of quicklime and calcium sulfoaluminate.
[4] The radically polymerizable resin composition according to any one of [1] to [3], wherein the radical polymerization initiator (C) is a hydroperoxide.
[5] The radically polymerizable resin composition according to any one of [1] to [4], further comprising a metal-containing compound (E) and a thiol compound (F).
[6] The radically polymerizable resin composition according to any one of [1] to [5], wherein the swelling material (B) is 0.3 to 30 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A).
[7] The radically polymerizable resin composition according to any one of [1] to [6], wherein the radical polymerization initiator (C) is 0.1 to 10 parts by mass per 100 parts by mass of the radically polymerizable compound (A).
[8] A cured product of the radically polymerizable resin composition according to any one of [1] to [7 ].
Effects of the invention
According to the present invention, there can be provided a radical polymerizable resin composition having a small shrinkage rate, which is not limited by a molding method, a use temperature, an application, and the like, because the whole resin composition expands at a constant rate during curing and is then stable, by adding an appropriate amount of an expanding material to a radical polymerizable resin composition having a curing shrinkage rate caused by a decrease in the free volume of a liquid component during curing.
Further, a cured product of the radical polymerizable composition can be provided without impairing the fluidity.
Drawings
FIG. 1 is a graph showing the results of examples 1 to 4 and comparative example 1.
FIG. 2 is a graph showing the results of example 5 and comparative example 2.
FIG. 3 is a graph showing the results of comparative examples 7 and 8.
FIG. 4 is a graph showing the results of example 9 and comparative example 14.
FIG. 5 is a graph showing the results of example 1 and reference example 1.
FIG. 6 is a graph showing the results of example 6 and comparative example 3.
FIG. 7 is a graph showing the results of example 7 and comparative example 4.
FIG. 8 is a graph showing the results of example 8 and comparative example 5.
FIG. 9 is a graph showing the results of examples 9 to 13.
FIG. 10 is a graph showing the results of examples 1 and 15 and comparative examples 10 to 15.
FIG. 11 is a graph showing the results of examples 1,16 to 20.
Detailed Description
The present invention will be described in detail below.
(radical polymerizable resin composition)
A radical polymerizable resin composition according to an embodiment of the present invention includes a radical polymerizable compound (a), an expandable material (B), a radical polymerization initiator (C), and an aggregate (D), and the aggregate (D) includes cement.
< radically polymerizable Compound (A) >)
The radical polymerizable resin composition of the present invention uses the radical polymerizable compound (a) as a base material. In the present invention, the radical polymerizable compound (a) is a compound having an ethylenically unsaturated group in a molecule and undergoing a polymerization reaction by a radical.
Examples of the radical polymerizable compound (a) include a vinyl ester resin (epoxy (meth) acrylate resin), an unsaturated polyester resin, a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, a radical polymerizable unsaturated monomer, and a mixture of the above resin and the radical polymerizable unsaturated monomer, and among them, 1 or more compounds selected from the group consisting of a vinyl ester resin, an unsaturated polyester resin, and a mixture of the above resin and the radical polymerizable unsaturated monomer are preferable. Among these, vinyl ester resins are more preferable. In the present specification, the "(meth) acrylate" means "acrylate or methacrylate".
[ vinyl ester resin ]
As the vinyl ester resin, a resin obtained by reacting an unsaturated monobasic acid with an epoxy resin can be used.
Examples of the epoxy resin include a bisphenol epoxy resin, a biphenyl epoxy resin, a Novolac epoxy resin, a triphenylolmethane epoxy resin, an aralkyl bisphenol epoxy resin, a naphthalene epoxy resin, and an aliphatic epoxy resin. These may be used alone or in combination of two or more.
Examples of the bisphenol epoxy resin include a resin obtained by reacting a bisphenol with epichlorohydrin and/or methyl epichlorohydrin, a resin obtained by reacting a glycidyl ether of bisphenol a and a condensate of the bisphenol with epichlorohydrin and/or methyl epichlorohydrin, and the like. Examples of the bisphenols include bisphenol a, bisphenol F, bisphenol S, and tetrabromobisphenol a.
Examples of the biphenyl type epoxy resin include resins obtained by reacting biphenol with epichlorohydrin and/or methyl epichlorohydrin.
Examples of the Novolac type epoxy resin include resins obtained by reacting phenol Novolac or cresol Novolac with epichlorohydrin and/or methyl epichlorohydrin.
Examples of the triphenylolmethane type epoxy resin include resins obtained by reacting triphenylolmethane or trimethylphenol methane with epichlorohydrin and/or methyl epichlorohydrin.
Examples of the aralkyl bisphenol type epoxy resin include resins obtained by reacting an aralkyl phenol with epichlorohydrin and/or methyl epichlorohydrin.
Examples of the naphthalene epoxy resin include resins obtained by reacting dihydroxynaphthalene with epichlorohydrin and/or methyl epichlorohydrin.
Examples of the aliphatic epoxy resin include an alicyclic epoxy resin, an alicyclic diol diglycidyl ether epoxy resin, an aliphatic diol diglycidyl ether epoxy resin, and a poly (oxyalkylene) diol diglycidyl ether epoxy resin.
Examples of the alicyclic epoxy resin include alicyclic diepoxy acetals, alicyclic diepoxy adipates, and alicyclic diepoxy carboxylates.
Specific examples of the alicyclic diol diglycidyl ether include diglycidyl ethers of alicyclic diols having 3 to 20 carbon atoms (preferably 6 to 12 carbon atoms, and more preferably 7 to 10 carbon atoms) such as cyclohexanedimethanol diglycidyl ether, dicyclopentenyl diol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol a, and dihydroxyterpene diglycidyl ether. Among them, a commercially available product of cyclohexanedimethanol diglycidyl ether is "デナコール EX-216L" available from ナガセケムテックス K.K.
Specific examples of the aliphatic diol diglycidyl ether include diglycidyl ethers of aliphatic diols having 2 to 20 carbon atoms (preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms) such as 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Among them, commercially available 1, 6-hexanediol diglycidyl ether include "デナコール EX-212L" available from ナガセケムテックス K.K., "SR-16H" available from Saka chemical industry K.K., "SR-16 HL", and "エポゴーセー (registered trademark) HD" available from Nikko Kabushiki Kaisha. Further, a commercially available 1, 4-butanediol diglycidyl ether is available as "デナコール EX-214L" from ナガセケムテックス K.K.
Specific examples of the poly (oxyalkylene) glycol diglycidyl ether include diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly (tetramethylene) glycol diglycidyl ether, and the like.
Preferred examples of the aliphatic epoxy resin include 1, 6-hexanediol diglycidyl ether, diglycidyl ether of polyethylene glycol, and poly (tetramethylene) glycol diglycidyl ether. Among them, aliphatic epoxy resins having a number average molecular weight of 150 to 1000 are more preferable.
The epoxy resin may be a diglycidyl ester such as dimer acid diglycidyl ester or hexahydrophthalic acid diglycidyl ester. The epoxy resin may be obtained by reacting the epoxy resin with a diisocyanate and has
Figure BDA0003705313910000061
Oxazolidone ring epoxy resin. As having
Figure BDA0003705313910000062
Specific examples of the oxazolidone ring epoxy resin include AER4152 manufactured by Asahi Kasei エポキシ, アラルダイト (registered trademark).
As the unsaturated monobasic acid, known unsaturated monobasic acids can be used, and examples thereof include (meth) acrylic acid, crotonic acid, and cinnamic acid. In addition, a reactant of a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups and a polybasic acid anhydride may also be used. In the present specification, "(meth) acrylic" means one or both of "acrylic acid and methacrylic acid", and "(meth) acryloyl" means one or both of "acryloyl group and methacryloyl group".
The polybasic acid is used to increase the molecular weight of the epoxy resin, and a known polybasic acid can be used. Examples thereof include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol-2 mol maleic anhydride adduct, polyethylene glycol-2 mol maleic anhydride adduct, propylene glycol-2 mol maleic anhydride adduct, polypropylene glycol-2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6-ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, and carboxyl-terminal butadiene-acrylonitrile copolymer (trade name Hycar CTBN).
[ unsaturated polyester resin ]
As the unsaturated polyester resin, a resin obtained by esterification reaction of a dibasic acid component containing an unsaturated dibasic acid and a saturated dibasic acid used as needed, and a polyhydric alcohol component can be used.
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, and the like, and these may be used alone or in combination of 2 or more.
Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid, phthalic anhydride, halophthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic anhydride, dimer acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic anhydride, 4' -biphenyldicarboxylic acid, and aromatic dibasic acids such as dialkyl esters thereof, and halogenated saturated dibasic acids, and these may be used alone or in combination of 2 or more.
The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1, 2-cyclohexanediol, and mixtures thereof, Dihydric alcohols such as 1, 3-cyclohexanediol, 1, 4-cyclohexanedimethanol, p-xylylene glycol, dicyclohexyl-4, 4' -diol, 2, 6-decahydronaphthalene diol, and 2, 7-decahydronaphthalene diol;
dihydric alcohols such as adducts of 2-membered phenols represented by hydrogenated bisphenol a, cyclohexanedimethanol, bisphenol a, bisphenol F, bisphenol S, tetrabromobisphenol a and alkylene oxides represented by propylene oxide or ethylene oxide;
and trihydric or higher alcohols such as 1,2,3, 4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.
The unsaturated polyester may be modified with a dicyclopentadiene compound within a range not impairing the effects of the present invention. As the method of modification with a dicyclopentadiene-based compound, for example, a known method such as a method of obtaining an addition product of dicyclopentadiene and maleic acid (didecanol mono malate) and introducing the obtained adduct into a dicyclopentadiene skeleton using the obtained product as a monobasic acid is exemplified.
The vinyl ester resin or unsaturated polyester resin used in the present invention may be introduced with an oxidative polymerization (air-curing) group such as allyl group or benzyl group. The method of introduction is not particularly limited, and examples thereof include a method of adding a polymer having an oxidative polymerization group, a method of condensing a compound having a hydroxyl group and an allyl ether group, and a method of adding a reaction product of a compound having a hydroxyl group and an allyl ether group and an acid anhydride to allyl glycidyl ether or 2, 6-diglycidyl phenyl allyl ether.
In the present invention, the oxidative polymerization (air curing) means: crosslinking accompanied by generation and decomposition of a peroxide due to oxidation of a methylene bond located between an ether bond and a double bond, which is seen in, for example, an allyl ether group or the like.
[ polyester (meth) acrylate resin, urethane (meth) acrylate resin, and (meth) acrylate resin ]
As the polyester (meth) acrylate resin in the present invention, for example, a polyester obtained by reacting a polyvalent carboxylic acid with a polyvalent alcohol, specifically, a resin obtained by reacting (meth) acrylic acid with respect to hydroxyl groups at both ends of polyethylene terephthalate or the like can be used.
As the urethane (meth) acrylate resin, for example, a resin obtained by reacting (meth) acrylic acid with respect to hydroxyl groups or isocyanate groups at both ends of polyurethane (obtained by reacting isocyanate with polyol) can be used.
Examples of the (meth) acrylate resin include poly (meth) acrylate resins having 1 or more substituents selected from the group consisting of a hydroxyl group, an isocyanate group, a carboxyl group, and an epoxy group, and resins obtained by reacting (meth) acrylates having a hydroxyl group with a substituent of a polymer of a monomer having the substituent and a (meth) acrylate.
[ radical polymerizable unsaturated monomer ]
In the present invention, as the radical polymerizable compound (a), a radical polymerizable unsaturated monomer can be used.
The radical polymerizable unsaturated monomer may be used alone, but is preferably used in the form of a mixture of the radical polymerizable unsaturated monomer and at least 1 resin of the vinyl ester resin and the unsaturated polyester resin.
The radical polymerizable unsaturated monomer is not particularly limited, but is preferably a monomer having a vinyl group or a (meth) acryloyl group.
Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate, and the like.
Specific examples of the monomer having a (meth) acryloyl group include (meth) acrylates and the like. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, and mixtures thereof, Ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, neopentyl glycol di (meth) acrylate, the dimethacrylate of PTMG, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1, 3-dimethacryloxypropane, 2-bis [ 4- (methacryloylethoxy) phenyl ] propane, propylene glycol mono (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol mono (meth) acrylate, di (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol (meth) acrylate, 2-2, 2, 2-bis [ 4- (methacryloyloxy-diethoxy) phenyl ] propane, 2-bis [ 4- (methacryloyloxy-polyethoxy) phenyl ] propane, tetraethylene glycol diacrylate, bisphenol AEO-modified (n ═ 2) diacrylate, isocyanurate EO-modified (n ═ 3) diacrylate, pentaerythritol diacrylate monostearate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, and the like.
Further, examples of the polyfunctional (meth) acrylate include alkanediol di (meth) acrylates such as ethylene glycol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and the like; polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol (meth) acrylate; trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Further, as the radical polymerizable unsaturated monomer, the following compounds may be used. Specific examples thereof include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate, allyl methacrylate, vinylbenzylbutyl ether, vinylbenzylhexyl ether, vinylbenzyloctyl ether, vinylbenzyl (2-ethylhexyl) ether, vinylbenzyl (β -methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl (β -phenoxyethyl) ether, vinylbenzyldicyclopentenyl ether, vinylbenzyldicyclopentenyloxyethyl ether, vinylbenzyldicyclopentenyl methyl ether, and divinylbenzyl ether.
In addition to the above, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like can be mentioned.
These may be used alone, or 2 or more of them may be used in combination.
The radical polymerizable unsaturated monomer can be used for lowering the viscosity of the radical polymerizable resin composition of the present invention, improving the hardness, strength, chemical resistance, water resistance, and the like, but if the content is too large, deterioration of the cured product and environmental pollution may be caused. Therefore, the content of the radical polymerizable unsaturated monomer is preferably 90% by mass or less in the radical polymerizable compound (a).
The radical polymerizable compound (a) may be a compound in which a catalyst and a polymerization inhibitor used in synthesizing a vinyl ester resin, an unsaturated polyester resin, a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, and a (meth) acrylate resin remain. Examples of the catalyst include tertiary nitrogen-containing compounds such as triethylamine, pyridine derivatives, and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; phosphorus compounds such as trimethylphosphine and triphenylphosphine, and the like.
Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, phenothiazine, and the like.
When a catalyst or a polymerization inhibitor remains in the radically polymerizable compound (a), the amount thereof is preferably 0.001 to 2 parts by mass per 100 parts by mass of the total of the vinyl ester resin and the unsaturated polyester resin.
The content of the radical polymerizable compound (a) in the radical polymerizable resin composition of the present invention is preferably 5 to 99.9% by mass, more preferably 10 to 80% by mass, even more preferably 15 to 60% by mass, and even more preferably 18 to 40% by mass. When the content of the radical polymerizable compound (a) in the radical polymerizable resin composition is within the above range, the hardness of the cured product is further improved.
< intumescent Material (B) >
The expansion material (B) used in the present invention may be any expansion material as long as it is an expansion material that is generally used as an expansion material for concrete and satisfies the standard of JIS a 6202 "expansion material for concrete". Specifically, the material may be one that can generate calcium hydroxide and ettringite by hydration reaction. For example, the swelling material (B) preferably contains at least 1 material selected from the group consisting of quicklime and calcium sulfoaluminate. More preferable examples of the expanding material include (1) an expanding material containing quicklime as an active ingredient (quicklime-based expanding material), (2) an expanding material containing calcium sulfoaluminate as an active ingredient (ettringite-based expanding material), and (3) a quicklime-ettringite composite-based expanding material.
Specific examples of the quick lime-based expansive material include the Pacific ハイパーエクスパン -K, Pacific ハイパーエクスパン -M, Pacific エクスパン -K, Pacific エクスパン -M, and Pacific N-EX manufactured by Pacific マテリアル.
Specific examples of the ettringite-based expansion material include デンカ CSA #10 and デンカ CSA #20 manufactured by デンカ.
Specific examples of the quicklime-ettringite composite intumescent material include デンカ -manufactured デンカ パ ワ ー CSA type S, デンカ パ ワ ー CSA type R, デンカ パ ワ ー CSA type T, and the like.
The content of the expanding material (B) of the present invention is preferably 0.3 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 0.7 to 20 parts by mass, and most preferably 1 to 16 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a). When the content of the swelling material (B) is 30 parts by mass or less, the swelling ratio does not exceed the elongation of the resin when the radical polymerizable resin composition is cured. On the other hand, if the content of the swelling material (B) is 0.3 parts by mass or more, the swelling performance with respect to the radical polymerizable compound (a) is not exhibited in some cases. These expansion materials (B) may be used alone or in combination of 2 or more.
< radical polymerization initiator (C) >)
The radical polymerizable resin composition of the present invention contains a radical polymerization initiator (C) as a curing agent. Examples of the radical polymerization initiator (C) include a thermal radical polymerization initiator (C1) and a photo radical polymerization initiator (C2). Among them, a thermal radical polymerization initiator (C1) is preferable.
Examples of the thermal radical polymerization initiator (C1) include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butyl peroxybenzoate, Hydroperoxide systems such as Cumene Hydroperoxide (CHP: Cumene Hydroperoxide), diisopropylbenzene Hydroperoxide, t-butyl Hydroperoxide, Hydroperoxide systems such as p-menthane Hydroperoxide (RCOOH, Hydroperoxide), dialkyl peroxides such as diisopropylbenzene peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters, and organic peroxides such as percarbonate. Among them, preferred is a hydroperoxide-based radical polymerization initiator (RCOOH) (also simply referred to as hydroperoxide), and more preferred is Cumene Hydroperoxide (CHP) such as パークミル (registered trademark) H-80 manufactured by nippon oil co., ltd., and diisopropylbenzene hydroperoxide such as パークミル (registered trademark) P manufactured by nippon oil co., ltd.
Examples of the photo radical polymerization initiator (C2) include benzoin ether systems such as benzoin alkyl ether, benzophenone systems such as benzophenone, benzil, and methyl benzoylbenzoate, benzophenone systems such as benzil dimethyl ketal, 2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, acetophenone systems such as 1, 1-dichloroacetophenone, and thioxanthone systems such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.
Examples of the photo radical polymerization initiator (C2) having photosensitivity in the ultraviolet to visible light region include known initiators represented by acetophenone, benzil ketal, and (bis) acylphosphine oxide, and specifically include: trade name イルガキュア -1700 (manufactured by チバスペシャルティーケミカルズ) obtained by mixing 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: manufactured by Darocur1173, チバスペシャルティーケミカルズ) and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide (manufactured by チバスペシャルティーケミカルズ) at a ratio of 75%/25%; trade name イルガキュア ー 1800 (manufactured by チバスペシャルティーケミカルズ) obtained by mixing 1-hydroxycyclohexyl phenyl ketone (manufactured by イルガキュア ー 184, チバスペシャルティーケミカルズ) and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide (manufactured by チバスペシャルティーケミカルズ) at a ratio of 75%/25%, and trade name イルガキュア ー 1850 (manufactured by チバスペシャルティーケミカルズ) obtained by mixing at a ratio of 50%/50%; bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: イルガキュア ー 819, チバスペシャルティーケミカルズ, manufactured by LTD.); 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF corporation); and a trade name Darocur4265 obtained by mixing 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur1173, チバスペシャルティーケミカルズ, manufactured by Kabushiki Kaisha) with 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF, manufactured by Kabushiki Kaisha) at a ratio of 50%/50%.
Examples of the photo-radical polymerization initiator (C2) having photosensitivity in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, dicyclopentyldiethyltitanium-bis (pentafluorophenyl) and the like.
These radical polymerization initiators (C) may be used alone or in combination of 2 or more. The other reaction may be introduced for the purpose of assisting the reaction which is the main one of the thermal curing and the photo curing, or a thermal radical polymerization initiator (C1) and a photo radical polymerization initiator (C2) may be used in combination as necessary.
Further, depending on the molding conditions, the organic peroxide/pigment system, the diphenyliodide/pigment system, the imidazole/ketone compound, the hexaallylbiimidazole compound/hydrogen donating compound, the mercaptobenzothiazole/thiopyran
Figure BDA0003705313910000141
Salt, metal arene/cyanine pigment, hexaallylbiimidazole/radical generator, etc.
When the radical polymerizable resin composition of the present invention contains the radical polymerization initiator (C), the amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8.0 parts by mass, even more preferably 0.3 to 6.0 parts by mass, and most preferably 0.3 to 5.0 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (a).
< aggregate (D) >, and
the radical polymerizable resin composition of the present invention comprises an aggregate (D) containing cement. The aggregate (D) other than cement is not particularly limited, and an aggregate used for mortar and concrete can be used. The aggregate other than cement is not particularly limited, and examples thereof include calcium carbonate, crushed stone, sandstone, gypsum, marble, quartz, limestone, silica sand, silica, river sand, and the like. From the viewpoint of weight reduction, a lightweight aggregate such as sintered shale, silicic acid-based spheres, and nonsilicic acid-based spherical perlite may be used. Among them, silica sand is preferable, and silica sand No. 7 and silica sand No. 8 are more preferable.
As the cement, portland cement, other mixed cement, ultra-fast hardening cement, and the like can be used without particular limitation. Examples of the portland cement include low-heat portland cement, medium-heat portland cement, ordinary portland cement, early strength portland cement, super early strength portland cement, and sulfate-resistant portland cement. The blended cement may be blast furnace cement, fly ash cement, silica cement, or the like. Among them, inexpensive portland cement is preferable, and early-strength and super-early-strength portland cement is more preferable. As for these cements, the cements exemplified above may be used in the form of a single body, or those obtained by mixing in any combination and in any mixing ratio may be used.
Calcium carbonate is transparent in a coating film, functions as an extender pigment that does not hide a coated surface (substrate surface), and has effects such as filling of recesses and reduction of coating cost. As the calcium carbonate, there is commercially available, for example, TM-2 (manufactured by Hakka Kogyo Co., Ltd.).
Since calcium carbonate has a specific particle size distribution, is excellent in dispersibility, and is also porous, the specific gravity of the aggregate itself can be reduced, so that the aggregate is less likely to collapse, and the film-forming property can be improved.
Examples of the silicic acid-based spheres include volcanic ash hollow spheres, perlite, glass (silica) spheres, and fly ash spheres. Examples of the non-silicic acid-based spheres include alumina spheres, zirconia spheres, and carbon spheres. Specific examples of perlite include No. パーライト FL-0 (trade name, manufactured by Furong パーライト Co., Ltd.), ハードライト B-03, ハードライト B-04, and ハードライト B-05 (trade name, manufactured by Showa chemical industry Co., Ltd.).
The content of the aggregate (D) in the composition of the present invention is not particularly limited, and is 330 to 800 parts by mass, preferably 350 to 800 parts by mass, and more preferably 370 to 450 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a). In particular, when the content of the aggregate is 330 parts by mass or more, practical fluidity can be ensured. When the content of the aggregate is 800 parts by mass or less, the amount of the attached spatula decreases, and the workability can be prevented from being lowered.
The content of cement in the aggregate (D) is not particularly limited, and is preferably 1 to 80 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the aggregate (D). In particular, when the content of the cement is 1 part by mass or more, the particle size distribution of the aggregate can be optimized, and the practical fluidity can be ensured. Further, when the content of cement is 80 parts by mass or less, stickiness due to deterioration of fluidity can be prevented.
< Metal-containing Compound (E) >)
The radical polymerizable resin composition of the present invention may use 1 or more metal-containing compounds (E) selected from the group consisting of metal soaps (E1) and metal complexes having a β -diketone skeleton (E2) as a curing accelerator. The metal soap (E1) in the present invention is a salt of a long-chain fatty acid or an organic acid other than a long-chain fatty acid, and a metal element other than potassium and sodium. The metal complex having a β -diketone skeleton (E2) in the present invention is a complex in which a compound having a structure in which 1 carbon atom exists between 2 carbonyl groups is coordinated to a metal element.
The content of the metal-containing compound (E) in the radical polymerizable resin composition is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 4 parts by mass, and still more preferably 0.005 to 3 parts by mass in terms of metal component, based on 100 parts by mass of the radical polymerizable compound (a). When the content of the metal-containing compound (E) in terms of metal components is within the above range, the curing proceeds rapidly even in water and in a humid atmosphere.
[ Metal soap (E1) ]
The long-chain fatty acid in the metal soap (E1) is not particularly limited, and is preferably a fatty acid having 6 to 30 carbon atoms, for example. Specifically, preferable examples thereof include octanoic acids such as heptanoic acid and 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, and naphthenic acids, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid.
In addition, citronellac acid, linseed oil fatty acid, soybean oil fatty acid, tall oil acid, and the like can be cited.
In addition, the organic acid other than the long-chain fatty acid in the metal soap (E1) is not particularly limited, but is preferably a weak acid compound which is soluble in an organic solvent and has a carboxyl group, a hydroxyl group, or an enol group.
Examples of the compound having a carboxyl group include carboxylic acids such as formic acid, acetic acid, and oxalic acid; citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, folic acid and other hydroxy acids; amino acids such as alanine and arginine; aromatic acids such as benzoic acid and phthalic acid.
Examples of the compound having a hydroxyl group or an enol group include ascorbic acid, alpha acid, imide acid, isoascorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, and phosphonic acid.
Among them, a long-chain fatty acid is preferable, a linear or cyclic saturated fatty acid having 6 to 16 carbon atoms or an unsaturated fatty acid having 6 to 16 carbon atoms is more preferable, octanoic acid, 2-ethylhexanoic acid and naphthenic acid are further preferable, and 2-ethylhexanoic acid and naphthenic acid are further more preferable.
Examples of the metal element constituting the metal soap (E1) include group 1 to group 2 metal elements such as lithium, magnesium, calcium, and barium (excluding potassium and sodium), group 3 to group 12 metal elements such as titanium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc, group 13 to group 14 metal elements such as aluminum, indium, tin, and lead, rare earth metal elements such as neodymium and cerium, and bismuth.
In the present invention, the metal element of group 2 to 12 is preferable, zirconium, barium, vanadium, manganese, iron, cobalt, copper, titanium, bismuth, calcium, lead, tin and zinc are more preferable, zirconium, manganese, iron, cobalt, copper, titanium, bismuth, calcium, lead, tin and zinc are further more preferable, and zirconium, manganese, cobalt, bismuth and calcium are further more preferable.
Specific examples of the metal soap (E1) include zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, calcium octylate, zinc octylate, vanadium octylate, lead octylate, tin octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate, and among these, zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, calcium octylate, lead octylate, tin octylate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate are more preferable. Among them, manganese octylate and cobalt octylate are particularly preferable. Specific examples of the cobalt octylate include ヘキソエートコバルト (the total cobalt content in the product is 8 mass%, molecular weight is 345.34) manufactured by toyoho chemical corporation. Specific examples of manganese octoate include ヘキソエートマンガン (the manganese content in the total product is 8 mass%, molecular weight is 341.35) manufactured by Tohon chemical Co., Ltd.
[ Metal Complex having beta-diketone skeleton (E2) ]
A metal complex (E2) having a β -diketone skeleton (hereinafter, also referred to as "metal complex (E2)"). Examples of the metal complex (E2) include those obtained by forming a complex with a metal, such as acetylacetone, ethyl acetoacetate, and benzoylacetone, and these metal complexes (E2) also exhibit the same functions as those of the metal soap (E1).
Examples of the metal element constituting the metal complex (E2) include the same metal elements as those of the metal soap (E1).
Specific examples of the metal complex (E2) include zirconium acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, dibutoxybis (acetylacetonate) titanium, iron acetylacetonate, and cobalt ethylacetoacetate, and among these, zirconium acetylacetonate, titanium acetylacetonate, and dibutoxybis (acetylacetonate) titanium are more preferable.
< thiol Compound (F) >)
The radical polymerizable resin composition of the present invention may contain 1 or more thiol compounds (F) selected from the group consisting of secondary thiol compounds (F-1) and tertiary thiol compounds (F-2). In the present invention, it is presumed that the thiol compound (F) has a function as a curing accelerator and coordinates in the vicinity of the metal-containing compound (E), thereby also having a function of preventing the inactivation of the metal by water.
The thiol compound (F) used in the present invention is not particularly limited as long as it is a compound having 1 or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule (hereinafter, each of these may be referred to as "secondary mercapto group" or "tertiary mercapto group"), but from the viewpoint of rapidly curing even in water and the viewpoint of preventing the metal of the metal-containing compound (E) from being inactivated by water, a polyfunctional thiol which is a compound having 2 or more secondary or tertiary mercapto groups in the molecule is preferable, and among these, a 2-functional thiol which is a compound having 2 secondary or tertiary mercapto groups in the molecule is preferable. In addition, the secondary thiol compound (F-1) is more preferable than the tertiary thiol compound (F-2).
Here, the "polyfunctional thiol" refers to a thiol compound having 2 or more mercapto groups as functional groups, and the "2-functional thiol" refers to a thiol compound having 2 mercapto groups as functional groups.
The compound having 2 or more secondary or tertiary mercapto groups in the molecule is not particularly limited, and for example, a compound having at least 1 structure represented by the following formula (Q), and having 2 or more secondary or tertiary mercapto groups in the molecule including the mercapto groups in the structure represented by the following formula (Q) is preferable.
Figure BDA0003705313910000181
(in the formula (Q), R 1 Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, R 2 An alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms, wherein the above-mentioned group is bonded to an arbitrary organic group. a is an integer of 0 to 2. )
[ Secondary thiol Compound (F-1) ]
When the thiol compound (F) having a structure represented by the formula (Q) is a secondary thiol compound (F-1), specific examples thereof include 3-mercaptobutyric acid, bis (1-mercaptoethyl) 3-mercaptophthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), and the like, Dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), Ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), hydrogenated bisphenol a bis (3-mercaptobutyrate), bisphenol a dihydroxyethyl ether-3-mercaptobutyrate, 4' - (9-fluorenylidene) bis (2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), Diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-phenylpropionate), trimethylolpropane tris (3-mercapto-3-phenylpropionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), dipentaerythritol hexa (3-mercapto-3-phenylpropionate), and the like.
Among the secondary thiol compounds (F-1), commercially available products of compounds having 2 or more secondary mercapto groups in the molecule include 1, 4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko K.K., カレンズ MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K., カレンズ MT (registered trademark) PE1), 1,3, 5-tris [2- (3-mercaptobutyryloxyethyl) ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by Showa Denko K.K., カレンズ MT (registered trademark) NR1), trimethylolethane tris (3-mercaptobutyrate) (manufactured by Showa Denko K K.K., TEMB), trimethylolpropane tris (3-mercaptobutyrate) (manufactured by Showa Denko K.K.), TPMB), etc., preferably 1 or more of these compounds. Among them, 1, 4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko K.K., カレンズ MT (registered trademark) BD1) is preferable.
[ tertiary thiol Compound (F-2) ]
When the thiol compound (F) having a structure represented by the formula (Q) is a tertiary thiol compound (F-2), specific examples thereof include di (2-mercaptoisobutyl) phthalate, ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), di (3-mercapto-3-methylbutyl) phthalate, and mixtures thereof, Ethylene glycol bis (3-mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methylbutyrate), diethylene glycol bis (3-mercapto-3-methylbutyrate), butanediol bis (3-mercapto-3-methylbutyrate), octanediol bis (3-mercapto-3-methylbutyrate), trimethylolethane tris (3-mercapto-3-methylbutyrate), trimethylolpropane tris (3-mercapto-3-methylbutyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaerythritol hexa (3-mercapto-3-methylbutyrate), and the like.
The total amount of the thiol compounds (F) in the radical polymerizable resin composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, even more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 4 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a). When the amount of the thiol compound (F) is 0.01 parts by mass or more, a sufficient curing function can be obtained, and when the amount of the thiol compound (F) is 10 parts by mass or less, curing is rapidly performed.
The molar ratio [ (F)/(E) ] of the thiol compound (F) to the metal component of the metal-containing compound (E) is preferably 0.1 to 15, more preferably 0.3 to 10, still more preferably 0.6 to 8, still more preferably 0.8 to 5 in one embodiment of the present invention, and more preferably 0.5 to 15, still more preferably 1 to 12, still more preferably 1.5 to 10, and still more preferably 2 to 9 in another embodiment of the present invention. When the molar ratio [ (F)/(E) ] is 0.1 or more, the thiol compound (F) can be sufficiently coordinated in the vicinity of the metal-containing compound (E), and when the molar ratio is 15 or less, the balance between the production cost and the effect is improved.
The thiol compound (F) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the secondary thiol compound (F-1) and the tertiary thiol compound (F-2) are used in combination, the molar ratio [ (F-1)/(F-2) ] between the two compounds is preferably 0.001 to 1000, more preferably 1 to 10. If the molar ratio [ (F-1)/(F-2) ] is within the above range, the metal-containing compound (A) and the thiol compound (F) are stable in the radical polymerizable resin composition, and a disulfide compound is not generated as a by-product by bonding the thiol compounds (F) to each other. From the viewpoint of storing the radical polymerizable resin composition in a state in which the metal-containing compound (E) and the thiol compound (F) are stabilized, it is preferable to use the secondary thiol compound (F-1) or the tertiary thiol compound (F-2) alone.
< curing Accelerator (G) >)
The radical polymerizable resin composition of the present invention may contain a curing accelerator (G) other than the metal-containing compound (E) and the thiol compound (F) for the purpose of improving curability.
Examples of the curing accelerator (G) other than the metal-containing compound (E) and the thiol compound (F) include amines, and specifically, aniline, N-dimethylaniline, N-diethylaniline, p-toluidine, N-dimethyl-p-toluidine, N-bis (2-hydroxyethyl) p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [ N, N-bis (2-hydroxyethyl) amino ] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N-bis (2-hydroxypropyl) p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, and amines such as N, N-substituted anilines such as N-bis (hydroxyethyl) aniline and diethanolaniline, N-substituted p-toluidine, and 4- (N, N-substituted amino) benzaldehyde.
When the radically polymerizable resin composition of the present invention contains the curing accelerator (G), the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the radically polymerizable compound (a).
< fiber (H) >
The radical polymerizable composition of the present invention may contain a fiber as needed. Specific examples of the fibers usable in the present invention include glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polyolefin fibers, acrylic fibers, polyester fibers such as polyethylene terephthalate fibers, cellulose fibers, metal fibers such as steel fibers, and ceramic fibers such as alumina fibers. Among them, for example, polyolefin fibers may be used as the thixotropic agent. The thixotropic agent (thixotropy imparting agent) is a substance compounded for the purpose of imparting thixotropy.
Examples of the polyethylene-based fibers that are commercially available as polyolefin fibers include products of trade names such as ケミベスト (registered trademark) FDSS-2 (average fiber length of 0.6mm), ケミベスト (registered trademark) FDSS-5 (average fiber length of 0.1mm), ケミベスト (registered trademark) FDSS-25 (average fiber length of 0.6mm, hydrophilicized product), and ケミベスト (registered trademark) FDSS-50 (average fiber length of 0.1mm, hydrophilicized product) (all manufactured by mitsui petrochemical industry co.).
The carbon fiber is not particularly limited, and any known carbon fiber may be used. Examples thereof include polyacrylonitrile-based (PAN-based) carbon fibers, rayon-based carbon fibers, pitch-based carbon fibers, and the like. The carbon fibers may be used each alone or in combination of 2 or more. From the viewpoint of low cost and good mechanical properties, PAN-based carbon fibers are preferably used. Such carbon fibers are available as commercially available products. As the carbon fiber, Carbon Fiber Reinforced Plastic (CFRP) may be used.
The diameter of the carbon fiber is preferably 3 to 15 μm, and more preferably 5 to 10 μm. The length of the carbon fiber is usually 5 to 100 mm. In the present invention, the carbon fiber may be cut into pieces of 10.0 to 100.0mm, and further 12.5 to 50.0 mm.
These fibers are preferably used in the form of a fiber structure, biaxial web or triaxial web selected from, for example, plain weave, satin weave, nonwoven fabric, felt, roving, chopped strand, woven fabric, braid and composite structures thereof. For example, the fiber structure may be used by impregnating the fiber structure with a radical polymerizable composition, and optionally, pre-polymerizing the composition to form a prepreg.
As the mesh, for example, a biaxial mesh or a triaxial mesh is used. The length (mesh size) of one side of the square of the biaxial net and the length (mesh size) of one side of the regular triangle of the triaxial net are each preferably 5mm or more, and more preferably 10 to 20 mm. By using a biaxial net or a triaxial net, a curable material for preventing concrete peeling which is lightweight and excellent in economy, workability, and durability can be obtained.
These fibers are preferably used for enhancing the coating performance such as the resistance to peeling of concrete and the water repellency of FRP, or for producing FRP molded articles.
Among the fibers, glass fibers, cellulose fibers and the like having excellent transparency are preferable from the viewpoint of enabling visual inspection of the deterioration state of the base from the outside in applications such as prevention of concrete peeling.
The content of such fibers is preferably 0.3 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and still more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a).
< polymerization inhibitor (I) >
The radical polymerizable resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the radical polymerizable compound (a) and from the viewpoint of controlling the reaction rate.
Examples of the polymerization inhibitor include known polymerization inhibitors such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-t-butylcatechol.
When the radical polymerizable resin composition contains the polymerization inhibitor (I), the amount thereof is 0.0001 to 10 parts by mass, and more preferably 0.001 to 1 part by mass, respectively, per 100 parts by mass of the radical polymerizable compound (a).
< curing retarder (J) >
The radical polymerizable resin composition of the present invention may contain a curing retarder for the purpose of retarding the curing of the radical polymerizable compound (a). Examples of the curing retarder include radical curing retarders, and examples thereof include TEMPO derivatives such as 2,2,6, 6-tetramethylpiperidine 1-oxyl (TEMPO), 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl (4H-TEMPO), and 4-Oxo-2, 2,6, 6-tetramethylpiperidine 1-oxyl (4-Oxo-TEMPO). Among them, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl (4H-TEMPO) is preferable in view of cost and ease of handling.
When the radically polymerizable resin composition contains the curing retarder (J), the amount thereof is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 1 part by mass, per 100 parts by mass of the radically polymerizable compound (a).
< Water reducing agent (L) >
The radical polymerizable resin composition of the present invention may contain a water reducing agent (L) that can be used and can impart water reducing properties, if necessary. As the water reducing agent, known water reducing agents used for concrete, such as liquid or powder water reducing agents, AE water reducing agents, high performance water reducing agents, and high performance AE water reducing agents, can be used without limitation.
The polycarboxylic acid-based water reducing agent is also suitable from the viewpoint of suppressing the decrease in concrete fluidity associated with the addition of the aluminum silicate having swelling property described above, maintaining good fluidity, and improving workability.
As the water reducing agent, known water reducing agents used for concrete, such as liquid or powder water reducing agents, AE water reducing agents, high performance water reducing agents, and high performance AE water reducing agents, can be used without limitation.
The polycarboxylic acid-based water reducing agent is also suitable from the viewpoint of suppressing the decrease in concrete fluidity associated with the addition of the aluminum silicate having swelling property described above, maintaining good fluidity, and improving workability.
The radical polymerizable resin composition preferably contains 0.1 to 3.0 mass% of a water reducing agent.
< other ingredients >
The radical polymerizable resin composition of the present invention may contain components other than the above components as long as the strength expression property and the acid resistance property of the cured product are not particularly impaired. Examples of the component that can be contained include, in addition to hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, admixtures that can be used in mortar or concrete and can impart properties such as setting control, acceleration of setting, delay of setting, thickening, water retention, defoaming, hydrophobicity, and water repellency; and an admixture for mortar or concrete, such as fibers made of a material such as metal, polymer or carbon, a pigment, an extender, a foaming agent, a clay mineral such as zeolite. Examples of the component that can be contained include a coupling agent, a plasticizer, an anion-immobilizing component, a solvent, a polyisocyanate compound, a surfactant, a wetting dispersant, a wax, and a thixotropic agent.
[ coupling agent ]
For the purpose of improving processability, improving adhesion to a base material, and the like, a coupling agent can be used for the radical polymerizable resin composition of the present invention. Examples of the coupling agent include known silane coupling agents, titanate coupling agents, and aluminum coupling agents.
Examples of such a coupling agent include R 3 -Si(OR 4 ) 3 The silane coupling agent is shown. R is defined as 3 Examples thereof include aminopropyl, glycidyloxy, methacryloyloxy, N-phenylaminopropyl, mercapto, vinyl and the like, as R 4 Examples thereof include methyl and ethyl.
When the radical polymerizable resin composition contains a coupling agent, the amount thereof is preferably 0.001 to 10 parts by mass per 100 parts by mass of the radical polymerizable compound (a).
[ plasticizer ]
The radical polymerizable resin composition of the present invention may be blended with a plasticizer as needed. The plasticizer is not particularly limited, and for the purpose of adjusting physical properties, and the like, there may be mentioned phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; nonaromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; trimellitates; polystyrenes such as polystyrene and poly-alpha-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon-based oils such as alkylbiphenyls and partially hydrogenated terphenyls; operating the oils; polyethers such as polyether polyols including polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and derivatives obtained by converting hydroxyl groups of these polyether polyols into ester groups, ether groups, and the like; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; polyester plasticizers obtained from 2-membered acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and 2-membered alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; and vinyl polymers obtained by polymerizing vinyl monomers by various methods, such as acrylic plasticizers.
Among them, it is preferable to add a polymeric plasticizer which is a polymer having a number average molecular weight of 500 to 15000, in view of adjusting the viscosity of the radical polymerizable composition and the mechanical properties such as tensile strength and elongation of a cured product obtained by curing the composition. Further, the polymer plasticizer is preferable because it can maintain the initial physical properties for a long period of time, as compared with the case of using a low-molecular plasticizer which is a plasticizer containing no polymer component in the molecule. The polymer plasticizer may have or may not have a functional group, although not limited thereto.
The number average molecular weight of the polymeric plasticizer is more preferably 800 to 10000, and still more preferably 1000 to 8000. When the number average molecular weight is 500 or more, the plasticizer can be inhibited from flowing out over time due to the influence of heat, rainfall, and water, and the initial physical properties can be maintained for a long period of time. Further, when the number average molecular weight is 15000 or less, an increase in viscosity can be suppressed, and sufficient workability can be ensured.
[ anion-immobilized component ]
In addition, hydrotalcite or hydrocalumite can be used for immobilizing anions such as chloride ions.
These hydrotalcites may be natural or synthetic, and may be used with or without surface treatment or crystal water. For example, a basic carbonate represented by the following general formula (R) may be mentioned.
M x ·Mg y ·Al Z CO 3 (OH) xr+2y+3z-2 ·mH 2 O (R)
(wherein M is an alkali metal or zinc, x is a number of 0 to 6, y is a number of 0 to 6, z is a number of 0.1 to 4, r is the valence of M, and M is the number of crystal water of 0 to 100.)
The hydrocalumite may be natural or synthetic, and may be used with or without surface treatment or crystal water. Examples thereof include those represented by the following general formulae (S) and (T).
3CaO·Al 2 O 3 ·CaX 2 ·kH 2 O (S)
(X is an anion having a valence of 1, k.ltoreq.20)
3CaO·Al 2 O 3 ·CaY·kH 2 O (T)
(Y is an anion having a valence of 2, k.ltoreq.20)
Furthermore, nitrite ions (NO) which are considered to have an effect of inhibiting corrosion of the steel reinforcement in the production stage are supported on the xonotlite 2 - ) Examples of the anion that can be supported include a nitrate ion (NO) 3 - ) Hydroxyl ion (OH) - ) Oxalate ion (CH) 3 COO - ) Carbonate ion (CO) 3 - ) Sulfate ion (SO) 4 2- ) And the like.
These hydrotalcites and hydrocalumites may be used in the form of a single body, but may be used by mixing into a cement slurry.
When mixed into a cement slurry, hydroxide ions (OH) which coexist during the hydration reaction are assumed - ) Or sulfate ions (SO) contained in cement 4 2- ) Various influences are exerted on the anion exchange reaction which is a characteristic of the xonotlite. From the viewpoint of maintaining the exchange reaction with the target chloride ion, hydrocalumites carrying nitrite ions are preferable.
[ solvent ]
In the radical polymerizable resin composition of the present invention, a solvent may be compounded as necessary. Examples of the solvent that can be mixed include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. These solvents may also be used in the manufacture of the polymer.
[ polyisocyanate Compound ]
The radical polymerizable resin composition of the present invention may contain a polyisocyanate compound. The polyisocyanate compound reacts with the hydroxyl group of the radically polymerizable compound (a) to form a cured coating film.
The polyisocyanate compound is a compound containing 2 or more isocyanate groups in the molecule, and the isocyanate groups can be blocked with a blocking agent or the like.
Examples of the polyisocyanate compound which is not blocked with a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2, 4 (or 2,6) -diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and 1,3- (isocyanatomethyl) cyclohexane; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; polyisocyanates such as 3-or more-membered polyisocyanates such as lysine triisocyanate, adducts of the above polyisocyanates with polyols, low-molecular weight polyester resins, water, etc., cyclic polymers (e.g., isocyanurates) of the above diisocyanates, biuret type adducts, etc. Among them, isocyanurate of hexamethylene diisocyanate is preferable.
These polyisocyanate compounds may be used alone or in combination of 2 or more.
When the radically polymerizable resin composition contains the polyisocyanate compound, the amount thereof is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 2 to 20 parts by mass, based on 100 parts by mass of the radically polymerizable compound (a).
The blocked polyisocyanate compound is a compound obtained by blocking an isocyanate group of the polyisocyanate compound with a blocking agent.
Examples of the blocking agent include phenol-based blocking agents such as phenol, cresol, and xylenol; epsilon-caprolactam; lactam systems such as delta-valerolactam, gamma-butyrolactam, and beta-propiolactam; alcohol systems such as methanol, ethanol, n-propanol or isopropanol, n-butanol, isobutanol or tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; oxime systems such as aminomethyloxime, acetaldoxime, acetoxime, methylethylketoxime, diacetylmonoxime, benzophenone oxime, and cyclohexanone oxime; active methylene blocking agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. By mixing the polyisocyanate and the blocking agent, the isocyanate group of the polyisocyanate can be easily blocked.
In the case where the polyisocyanate compound is an unblocked polyisocyanate compound, the reaction between the radically polymerizable compound (a) and the polyisocyanate compound in the radically polymerizable resin composition of the present invention is caused when the both are mixed, and therefore, it is preferable to separate the radically polymerizable compound (a) and the polyisocyanate compound in advance until the time of use and mix them at the time of use.
In order to react the radically polymerizable compound (a) with the polyisocyanate compound, a curing catalyst may be used. Examples of suitable curing catalysts include organic metal catalysts such as tin octylate, dibutyltin bis (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, and lead 2-ethylhexanoate.
When the radically polymerizable resin composition contains the curing catalyst in an amount, the amount is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 4 parts by mass, based on 100 parts by mass of the radically polymerizable compound (a).
[ surfactant ]
The radical polymerizable resin composition of the present invention may contain a surfactant.
Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone, or 2 or more of them may be used in combination.
Among these surfactants, 1 or more surfactants selected from anionic surfactants and nonionic surfactants are preferable.
Examples of the anionic surfactant include alkyl sulfate salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene alkyl ether sulfate ester salts such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; sulfonates such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, and potassium castor oil soap; naphthalene sulfonic acid formaldehyde condensate, special polymer system, etc.
Among them, preferred is a sulfonate, more preferred is sodium dialkylsulfosuccinate, and still more preferred is sodium dioctylsulfosuccinate.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol and other polyoxyethylene derivatives; sorbitan fatty acid esters such as polyoxyalkylene alkyl ethers, sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitan tetraoleate; glycerin fatty acid esters such as glycerin monostearate and glycerin monooleate.
Among them, preferred are polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and polyoxyethylene alkyl ether. The HLB (Hydrophile-lipophile Balance) of the nonionic surfactant is preferably 5 to 15, and more preferably 6 to 12.
When the radical polymerizable resin composition contains a surfactant, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a).
[ wetting dispersant ]
The radical polymerizable resin composition of the present invention may contain a wetting dispersant for the purpose of improving permeability to, for example, a repaired site which is wet or has not been in water.
The wetting dispersant includes a fluorine-based wetting dispersant and a silicone-based wetting dispersant, and these may be used alone or in combination of 2 or more.
Commercially available products of fluorine-based wetting dispersants include メガファック (registered trademark) F176, メガファック (registered trademark) R08 (manufactured by Dainippon インキ chemical industries, Ltd.), PF656, PF6320 (manufactured by OMNOVA), トロイゾル S-366 (manufactured by トロイケミカル Co., Ltd.), フロラード FC430 (manufactured by スリーエムジャパン Co., Ltd.), and polysiloxane polymer KP-341 (manufactured by shin-Etsu chemical industries, Ltd.).
Commercially available silicone-based wetting dispersants include BYK (registered trademark) -322, BYK (registered trademark) -377, BYK (registered trademark) -UV3570, BYK (registered trademark) -330, BYK (registered trademark) -302, BYK (registered trademark) -UV3500, BYK-306 (manufactured by ビックケミー & ジャパン Co., Ltd.), and silicone polymer KP-341 (manufactured by shin-Etsu chemical Co., Ltd.).
The silicone wetting dispersant preferably contains a compound represented by the following formula (U).
Figure BDA0003705313910000291
(in the formula, R 5 And R 6 Each independently represents a C1-12 hydrocarbon group containing an aromatic ring, or- (CH) 2 ) 3 O(C 2 H 4 O) p (CH 2 CH(CH 3 )O) q R 'and n are integers of 1 to 200, R' is an alkyl group having 1 to 12 carbon atoms, p and q are each an integer, and q/p is 0 to 10. )
Commercially available silicone wetting dispersants containing the compound represented by formula (U) include BYK (registered trademark) -302 and BYK (registered trademark) -322 (manufactured by ビックケミー & ジャパン).
When the radical polymerizable resin composition of the present invention contains a wetting dispersant, the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a).
[ wax ]
The radical polymerizable resin composition of the present invention may contain a wax.
The wax may be a paraffin wax or a polar wax, and these may be used alone or in combination of 2 or more.
As the paraffin, known paraffin having various melting points can be used. As the polar wax, a wax having a structure having both a polar group and a nonpolar group can be used, and specific examples thereof include NPS (registered trademark) -8070, NPS (registered trademark) -9125 (manufactured by japan ceresin co., ltd.), エマノーン (registered trademark) 3199, and エマノーン (registered trademark) 3299 (manufactured by kao corporation).
When the radical polymerizable resin composition of the present invention contains a wax, the amount thereof is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a). However, when the radical polymerizable resin composition of the present invention is used in water, there is a possibility that the wax may be eluted into the water, and therefore it is preferable not to use the wax.
[ thixotropic agent ]
For the purpose of viscosity adjustment for ensuring workability on vertical surfaces and ceiling surfaces, a thixotropic agent may be used for the radical polymerizable resin composition of the present invention.
Examples of the thixotropic agent include inorganic thixotropic agents and organic thixotropic agents, examples of the organic thixotropic agents include hydrogenated castor oil-based, amide-based, oxidized polyethylene-based, vegetable oil polymer-based, surfactant-based, and composite systems using these in combination, and specifically include DISPARLON (registered trademark) 6900-20X (manufactured by nakeh chemical co., ltd.).
Further, examples of the inorganic thixotropic agent include silica and bentonite, examples of the hydrophobic inorganic thixotropic agent include レオロシール (registered trademark) PM-20L (fumed silica manufactured by トクヤマ K.K.) and アエロジル (registered trademark) AEROSIL R-106 (Nippon アエロジル K.K.), and examples of the hydrophilic inorganic thixotropic agent include アエロジル (registered trademark) AEROSIL-200 (Nippon アエロジル K.K.). From the viewpoint of further improving the thixotropy, those obtained by adding BYK (registered trademark) -R605 and BYK (registered trademark) -R606 (manufactured by ビックケミー · ジャパン) as thixotropy modifiers to hydrophilic calcined silica can be suitably used. When the radical polymerizable resin composition of the present invention contains a thixotropic agent, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the radical polymerizable compound (a).
< water >)
The radical polymerizable resin composition of the present invention contains substantially no water from the viewpoint of obtaining a practical level of strength. That is, in the preparation of the radical polymerizable resin composition, no water is added as a constituent component of the composition. For example, the water content of the radical polymerizable resin composition is preferably less than 0.25 part by mass, more preferably 0.20 part by mass or less, further preferably 0.15 part by mass or less, and most preferably 0.10 part by mass or less, based on 100 parts by mass of the radical polymerizable compound (a).
< method for producing radical polymerizable resin composition >
The method for producing the radical polymerizable resin composition of the present invention is not particularly limited, and a method known in the art can be used. For example, the radical polymerizable resin composition can be produced as follows: the radical polymerizable compound (a) is mixed with the metal-containing compound (E) as needed, and further mixed with the radical polymerization initiator (C), the aggregate (D) containing cement, and the expanding material (B).
One embodiment of the method for producing a radical polymerizable resin composition of the present invention includes the steps of: a step (S1) of mixing a metal-containing compound (E) with the radical polymerizable compound (A) as required to obtain a resin product; a step (S2) of mixing a radical polymerization initiator (C) with the obtained resin product to obtain a curable resin product; and a step (S3) of mixing the aggregate (D) containing cement and the expanding material (B) with the obtained curable resin product to obtain a radical polymerizable resin composition.
In the step (S1) of obtaining a resin product (which may be simply referred to as the "step (S1)"), a polymerization inhibitor (I), a curing retarder (J), a thiol compound (F), and the like may be further mixed, if necessary, in addition to the metal-containing compound (E) to the radical polymerizable compound (a).
In the step (S3) (also simply referred to as "step (S3)") of obtaining a radical polymerizable resin composition, the aggregate (D) and the expanding material (B) containing cement are mixed with the curable resin product obtained in the step (S2) (also simply referred to as "step (S2)") of obtaining a curable resin product, and if necessary, a water reducing agent (L), fibers (H), and the like may be further mixed. Specific examples of the aggregate (D) include high-early strength portland cement, calcium carbonate TM-2, パーライト FL-0, ハードライト B-04, Yunzhou No. 5.5 silica sand, N50 silica sand, N40 silica sand, and N90 silica sand.
The radical polymerizable resin composition 6 produced in this way can be cured at room temperature, and is excellent in workability, early strength expression, and curability. Since the expandable material (B) is included, the shrinkage rate during curing is small, and the expansion rate of the cured product can be made larger than 0 depending on the conditions.
< cured product of radical polymerizable resin composition >
The cured product of the radical polymerizable resin composition of the present invention is obtained by curing the radical polymerizable resin composition described above.
[ curing method of radically polymerizable resin composition ]
When the radical polymerizable resin composition of the present invention contains a thermal radical polymerization initiator (C1), an example of a method for curing the radical polymerizable resin composition of the present invention is a curing method in which the radical polymerizable resin composition of the present invention is applied to the surface of a substrate and cured at room temperature. For example, the radical polymerizable resin composition of the present invention is used as a cross-sectional repair material for an inorganic structure. Since the radical polymerizable resin composition of the present invention contains the intumescent material (B), the obtained cured product does not shrink as much as before even after a certain period of time has elapsed.
Examples of the material of the substrate include thermosetting resins such as phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, vinyl ester resins, alkyd resins, polyurethanes, and polyimides in addition to concrete, asphalt concrete, mortar, brick, wood, and metal; thermoplastic resins such AS polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, テフロン (registered trademark), ABS resin, AS resin, and acrylic resin.
When the radical polymerizable resin composition of the present invention contains the photo radical polymerization initiator (C2), the following methods may be used as the timing of photo-curing: a method of applying a radical polymerizable resin composition to a base material and then photocuring the composition; a method in which a radical polymerizable resin composition is preliminarily polymerized (also referred to as B-staged or prepreg) to prepare a sheet, and the sheet is attached to a base material and then photocured.
The light source may be a light source having a spectral distribution in a photosensitive wavelength region of the photo radical polymerization initiator (C2), and for example, sunlight, an ultraviolet lamp, a near infrared lamp, a sodium lamp, a halogen lamp, a fluorescent lamp, a metal halide lamp, an LED, or the like may be used. Further, 2 or more types of photo radical polymerization initiators (C2) may be used in combination, and a wavelength cut filter may be used as a light source, or wavelengths required for preliminary polymerization and main polymerization may be used by using a specific wavelength of an LED. The wavelength used for the preliminary polymerization is desirably a long wavelength with a low energy level, and particularly, when near-infrared light is used, the polymerization degree can be easily controlled. In the present invention, the ultraviolet light (ultraviolet light) means light in a wavelength region of 280 to 380nm, the visible light (visible light) means light in a wavelength region of 380 to 780nm, and the near infrared light (near infrared light) means light in a wavelength region of 780 to 1200 nm. The irradiation time of the lamp required for the preliminary polymerization is affected by the effective wavelength region of the light source, the output, the irradiation distance, the thickness of the composition, and the like, and therefore cannot be defined as a whole, and for example, it is sufficient to irradiate for 0.01 hour or more, preferably for 0.05 hour or more.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples at all.
< method for measuring curing shrinkage >
The shrinkage/expansion ratio (change rate: negative is shrinkage, and positive is expansion ratio) of the cured product of the radical polymerizable resin composition of the present invention was measured in accordance with JIS A1129-3 (dial indicator method). The molded article (cured article) was prepared by molding according to the attached book a of JIS a 1129. A40X 160mm test specimen mold specified in JIS R5201 was used as the mold. A specimen of a cured product was molded by the method for producing a specimen for strength test specified in JIS R5201, 10, and after molding, the molded article was left to stand (cured) in a room at a temperature of 23 ℃. + -. 2 ℃ and a humidity of 50% while keeping a mold, and was released from the mold after about 24 hours from molding. Then, the measurement was started under the conditions shown in 4.3 of JIS A1129-3 using the instrument shown in 3 of JIS A1129-3 (time was set to 0).
Change amount (negative number: shrinkage, positive number: expansion) of the length of the long side at the time of elapse of time-the length of the long side (160mm) at the start (0 time) (1)
Change rate (negative number: shrinkage rate, positive number: expansion rate) change amount/length of long side (160mm) at start (0) (2)
The raw materials used for the production of the base polymerizable resin compositions in the examples and comparative examples are as follows.
< radically polymerizable Compound (A) >)
Radically polymerizable Compound (A-1)
Unsaturated polyester resin リゴラック (registered trademark), Showa Denko K.K., SR-110N (styrene content 40 mass%)
(Synthesis example 1)
"Synthesis of radically polymerizable Compound (A-2)"
150.4g of AER-2603 (bisphenol A epoxy resin manufactured by Asahi Kasei Co., Ltd.: epoxy equivalent 189), 188.4g of SR-16H (1, 6-hexanediol diglycidyl ether manufactured by Saka chemical Co., Ltd.), 0.255g of methylhydroquinone, and 1.5g of DMP-30 (2,4, 6-tris (dimethylaminomethyl) phenol manufactured by Tokyo chemical Co., Ltd.) were added to a 1L four-necked separable flask equipped with a stirrer, reflux condenser, gas inlet and thermometer, and the temperature was raised to 110 ℃. After the temperature was raised to 110 ℃ and 172g of methacrylic acid (manufactured by Mitsubishi レイヨン Co., Ltd.) was added dropwise over about 30 minutes, the reaction was allowed to proceed for about 4 hours, and the reaction was terminated at a time when the acid value became 10mgKOH/g, whereby a vinyl ester compound was obtained.
Next, 256.3g of dicyclopentenyloxyethyl methacrylate (FA-512 MT, manufactured by Hitachi chemical Co., Ltd.) and 85.4g of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi chemical Co., Ltd.) were added as radical polymerizable unsaturated monomers to obtain a non-styrene type radical polymerizable compound (A-2) having a viscosity of 280 mPas at 25 ℃ and an ester compound component ratio of 60 mass%.
< intumescent Material (B) >
B-1: as a quicklime-based expansive material, Pacific ハイパーエクスパン ー K (for structure) made from Pacific マテリアル
B-2: as the quicklime-based intumescent material, Pacific N-EX (early strength intumescent material) manufactured by Pacific マテリアル
B-3: as an ettringite-based intumescent material, デンカ CSA #10 manufactured by デンカ
B-4: as a composite expanding material of quicklime-ettringite, デンカ -made デンカ パ ワ ー CSA type S
< radical polymerization initiator (C) >)
As the thermal radical polymerization initiator, (C-1) Cumene Hydroperoxide (CHP) manufactured by Nichikoku K.K., パークミル (registered trademark) H-80 was used.
As the thermal radical polymerization initiator, (C-2) diisopropylbenzene hydroperoxide, manufactured by Nichikoku K.K., パークミル (registered trademark) P was used.
As the thermal radical polymerization initiator, (C-3) benzoyl peroxide, Nichikoku K.K., ナイパー (registered trademark) NS was used.
As the thermal radical polymerization initiator, (C-4) methyl ethyl ketone peroxide, manufactured by Nichikoku K.K., パーメック (registered trademark) N was used.
< aggregate (D) >
Aggregate (D-I):
early strength portland cement
Calcium carbonate TM-2
パーライト FL-0
ハードライトB-04
Silica sand No. 5.5 Yunzhou
N50 silica sand
N40 silica sand
Aggregate (D-II):
ボンド P mortar aggregate manufactured by コニシ society (including high early strength portland cement)
< Metal-containing Compound (E) >)
As the metal soap, (E-1) cobalt octylate (ヘキソエートコバルト, manufactured by Tohon chemical Co., Ltd., cobalt content in the total amount of the product was 8 mass%, molecular weight was 345.34) was used.
Manganese (E-2) octoate (ヘキソエートマンガン, manufactured by Tohony chemical Co., Ltd., manganese content in the total amount of the product was 8 mass%, molecular weight was 341.35) was used as the metal soap.
< thiol Compound (F) >)
As the secondary thiol compound (F-1), カレンズ MT (registered trademark) BD1(1, 4-bis (3-mercaptobutyryloxy) butane having a molecular weight of 299.43) was used as a 2-functional secondary thiol.
< curing Accelerator (G) >)
As the curing accelerator (G-1), dimethylaniline (DMA, manufactured by Tokyo chemical industry Co., Ltd.) was used.
< fiber (H) >
ケミベスト (registered trademark) FDSS-5
Multi-branched polyolefin fiber manufactured by Mitsui chemical ファイン
< polymerization inhibitor (I) >
As the polymerization inhibitor (I-1), tert-butylcatechol was used.
As the polymerization inhibitor (I-2), dibutylhydroxytoluene was used.
< curing retarder (J) >
4-H-TEMPO was used.
< epoxy resin >
The main agent is as follows: epoxy resin ボンド E208W, コニシ (available from Inc.)
Curing agent: curing agent for epoxy resin, ボンド E208W, コニシ
(example 1)
"preparation of a radically polymerizable resin composition"
(1) Step (S1):
a resin product was prepared by thoroughly mixing the metal-containing compound (E), the thiol compound (F), the polymerization inhibitor (I) and the curing retarder (J) with the radical polymerizable compound (A-2) obtained in Synthesis example 1 at the mixing amounts shown in Table 1.
(2) Step (S2):
a radical polymerization initiator (C) was mixed in the amount shown in table 1 with the resin product obtained in step (S1) to prepare a curable resin product.
(3) Step (S3):
in the curable resin product obtained in the step (S2), the expandable material (B), the aggregate (D), and the fibers (H) were thoroughly mixed in the respective components and mixing amounts shown in table 1, to obtain the radical polymerizable resin composition of the present example.
The mixing conditions in each step are as follows.
The stirrer: HOMEGENIZING DISPER Model 2.5 (manufactured by プライミクス Co., Ltd.)
Stirring speed: 3000 to 5000rpm
Temperature: 25 deg.C
Production of cured product of radically polymerizable resin composition "
The obtained radical polymerizable resin composition was poured into a 40X 160mm mold, left to stand (cured) in a room at a temperature of 23 ℃ C. + -. 2 ℃ and a humidity of 50% while maintaining the mold in a state, and was cured, and was released from the mold after about 24 hours from the molding. A cured product of the radical polymerizable resin composition of the present example was obtained.
Evaluation of shrinkage/expansion Properties of cured product "
The cured product of the obtained radical polymerizable resin composition was evaluated by the above-described evaluation method. The results are shown in FIG. 1.
"evaluation of flowability of resin composition"
The flowability of the resin composition was evaluated using a glue gun (ウルトラポイントガン) sold by ピーシーコックス japan sellable corporation.
The object to be evaluated was the radical polymerizable resin composition mixed in the step (S3).
A free radical polymerizable resin composition (200 g) was charged into a gun and a bar was set in accordance with a predetermined operation. Then, the trigger was pulled to determine whether or not the radical polymerizable resin composition was discharged from the tip of the nozzle.
The evaluation was "good" when the radical polymerizable resin composition was obtained, and the evaluation was "poor" when the radical polymerizable resin composition was not obtained. The case where the radical polymerizable resin composition mixed in the step (S3) was separated and only the resin was obtained was evaluated as "Δ". The results are shown in Table 1.
(examples 2 to 13, 15 to 20, comparative examples 1 to 6, and 10 to 15)
A radical polymerizable resin composition was obtained in the same manner as in example 1, except that the components and blending amounts shown in table 1 were used. In addition, a cured product of the radical polymerizable resin composition was produced in the same manner as in example 1. Then, the shrinkage/expansion properties of the cured products obtained were evaluated in the same manner as in example 1. The results are shown in FIGS. 1 to 2,6 to 9, 10 and 11.
(reference example 1)
A radical polymerizable resin composition was obtained in the same manner as in example 1, except that in the step (S3), a product obtained by mixing 10 parts by mass of water with respect to 100 parts by mass of the resin product in the curable resin product obtained in the step (S2) was used. In addition, a cured product of the radical polymerizable resin composition was produced in the same manner as in example 1. Then, the shrinkage/expansion properties of the cured product were evaluated in the same manner as in example 1. The results are shown in FIG. 5.
(comparative examples 7 and 8)
Epoxy resin compositions were obtained by using the aggregate (D-II) shown in Table 2 and an epoxy resin in place of the radical polymerizable composition of example 1. In addition, a cured product of the epoxy resin composition was produced by the following method. Then, the shrinkage/expansion properties of the cured products obtained were evaluated in the same manner as in example 1. The results are shown in FIG. 3.
(example 14 and comparative example 9)
A radical polymerizable resin composition was obtained in the same manner as in example 1, except that the components and blending amounts shown in table 2 were used. In addition, a cured product of the radical polymerizable resin composition was produced in the same manner as in example 1. Then, the shrinkage/expansion properties of the cured products obtained were evaluated in the same manner as in example 1. The results are shown in FIG. 4.
Production of cured product of epoxy resin composition "
After a main agent of an epoxy resin and a curing agent were sufficiently mixed, an aggregate (D-II) and early strength portland cement were mixed, the mixture was poured into a 40X 160mm mold, and the mold was left to stand (cured) in a room having a temperature of 23 ℃ C. + -. 2 ℃ and a humidity of 50% while maintaining the state of the mold, followed by curing and demolding at about 24 hours after molding. A cured product of the epoxy resin composition of this comparative example was obtained.
[ Table 1]
Figure BDA0003705313910000391
The symbols of the components in table 1 have the following meanings.
A-1 リゴラック (registered trademark) SR-110N
E-1 cobalt Octanoate
I-1 tert-butylcatechol
I-2-Dibutylhydroxytoluene
J-1 4H-TEMPO
G-1 Dimethylaniline
C-1 パークミル (registered trademark) H-80
C-2 パークミル (registered trademark) P
C-3 ナイパー (registered trademark) NS
C-4 パーメック (registered trademark) N
B-1 Pacific ハイパーエクスパン ー K (for structure)
B-2 Pacific ocean N-EX (early strength expansion material)
B-3 デンカCSA#10
B-4 デンカ パ ワ ー CSA model S
d-1 early strength portland cement
d-2 calcium carbonate TM-2
Number d-3 パーライト FL-0
d-4 ハードライトB-04
No. 5.5 silica sand of d-5 Yunzhou
d-6N 90 silica sand
d-7N 50 silica sand
d-8N 40 silica sand
d-9N 70 silica sand
[ Table 2]
Figure BDA0003705313910000411
[ Table 3]
Figure BDA0003705313910000421
FIG. 1 is a graph showing the results of examples 1 to 4 and comparative example 1. The volume shrinkage of the cured product of the radical polymerizable resin composition of comparative example 1 containing no swelling material (B) was observed. On the other hand, the radical polymerizable resin compositions of examples 1 to 3 containing the swelling material (B) were observed to swell in volume of the cured product thereof. In addition, with respect to the radical polymerizable resin composition of example 4, volume shrinkage was observed in about 0.5 hour from the start of curing, and then volume expansion was observed.
FIG. 2 is a graph showing the results of example 5 and comparative example 2. For comparison, example 1 and comparative example 1 of fig. 1 are also shown. From the results of fig. 2, it is clear that the effect of adding the swelling material (B) of the present invention is independent of the kind of radical polymerization initiator.
Fig. 3 is a graph showing the results of comparative example 7 and comparative example 8. The epoxy resin compositions of comparative examples 7 and 8 did not contain the radical polymerization initiator (C). The volume expansion effect as in example 1 was not observed in comparative example 8 containing the expanding material (B). That is, in the system without the radical polymerization initiator (C), no swelling effect is observed even if the swelling material (B) is contained.
FIG. 4 is a graph showing the results of example 9 and comparative example 14. Even when an aggregate (D-II) different from the aggregate (D-I) was used, the same volume expansion effect as in example 1 was observed in example 9.
Fig. 5 is a graph showing the results of example 1 and reference example 1. The test was conducted in a state where 10 parts by mass of water was positively mixed with 100 parts by mass of the resin product. It is found that when water is mixed, the initial swelling effect is remarkably greater than that when water is not mixed. Reference example 1 is a test example in which water is added in an amount that is not practical for the purpose of showing the effects of example 1. It is predicted that the strength of the cured product obtained in reference example 1 is greatly reduced, and the balance of various performances (water resistance, salt damage resistance, etc.) cannot be obtained.
Fig. 6 is a graph showing the results of example 6 and comparative example 3. Example 6 and comparative example 3 did not contain the thiol compound (F) and the curing retarder (J-1). The swelling effect was confirmed in example 6 containing the swelling material, and the swelling effect was not confirmed in comparative example 3 containing no swelling material. Therefore, it was found that the thiol compound (F) and the curing retarder (J-1) did not react with the swelling material.
FIG. 7 is a graph showing the results of example 7 and comparative example 4. Example 7 and comparative example 4 did not contain the metal-containing compound (E) and the thiol compound (F). The curing accelerator (G) and the polymerization inhibitor (I) are contained in different types. The swelling effect was confirmed in example 7 containing the swelling material, and the swelling effect was not confirmed in comparative example 4 containing no swelling material. Therefore, it is understood that the metal-containing compound (E) does not react with the intumescent material, and does not depend on the type of the polymerization inhibitor (I) and the presence or absence of the curing accelerator (G).
FIG. 8 is a graph showing the results of example 8 and comparative example 5. The radical polymerizable compound (a) in example 8 and comparative example 5 is different from others, and the metal-containing compound (E) is different from others. The radical polymerization initiator (C) is also different from others. Example 8 containing an intumescent material clearly had an intumescent effect when compared to comparative example 5 which did not contain an intumescent material. Therefore, it is found that the swelling effect is not dependent on the kinds of the radical polymerizable compound (A) and the metal-containing compound (E).
FIG. 9 is a graph showing the results of examples 9 to 13. Examples 9 to 13 are examples in which the amount of the expanding material added was increased or decreased as compared with example 1. It is understood that the swelling effect varies depending on the amount of the swelling material, and the swelling effect increases as the amount of the swelling material increases.
FIG. 10 is a graph showing the results of examples 1 and 15 and comparative examples 10 to 15. FIG. 11 is a graph showing the results of examples 1 and 16 to 20. Examples 15 to 20 and comparative examples 10 to 15 are examples in which the total amount of the aggregate (D) was increased or decreased as compared with example 1. In examples 15 to 20, the volume expansion effect was observed in the same manner as in example 1, but in comparative examples 10 to 15, the volume expansion effect was not observed.
The results of the fluidity evaluation by the gun for applying glue described in the lower part of tables 1 and 2 are shown. In example 13 and comparative examples 6, 7 and 8, the radical polymerizable resin composition did not come out even if the nozzle for applying the adhesive gun was pulled. In example 14 and comparative example 9, only the radical polymerizable compound (a) was extruded when the nozzle of the gun was pulled.
In example 13, the amount of the swelling material added was extremely large, which is considered to extremely deteriorate the fluidity as a radical polymerizable resin composition. In comparative example 6, the early strength portland cement was removed from example 1, and the portion was replaced with the aggregate (D-I). As a result, it is considered that the fluidity of the system to which the early strength portland cement is not added is deteriorated.
Furthermore, in comparative examples 7 and 8, the main agent of the epoxy resin, the curing agent and the aggregate (D-II) were mixed, and it is considered that the flowability as an epoxy resin composition was excessively poor.
In comparative example 9 and example 14, using the aggregate (D-II), and in the same way as in comparative examples 7 and 8, the presence or absence of the expanding material almost did not cause fluidity, and unlike the main agent and the curing agent of the epoxy resin, it is considered that only the radical polymerizable compound (A) was extruded without the nozzle pressure of the adhesive gun.
The measurement of the expansion/contraction ratio (change rate: negative number is contraction ratio, positive number is expansion ratio) of the present invention is carried out as follows: after molding, the molded article was left to stand (cured) in a room at a temperature of 23 ℃. + -. 2 ℃ and a humidity of 50%, and after demolding was carried out for about 24 hours, the molding was carried out under the conditions shown in 4.3 of JIS A1129-3 with the time set to 0. That is, the conditions during the test were 20. + -. 2 ℃ and (60. + -. 5)% relative humidity. Under these conditions, it was confirmed that the radical polymerizable resin compositions of examples 1 to 4 contained the swelling material (B), and therefore, even when water was not added to the reaction system, volume swelling was observed. In particular, examples 1 to 3, which contained an intumescent material having a quicklime component, had higher expansion ratios than example 4. Further, it is also known that the radical polymerization initiator (C) is an essential component.
According to the results of the present invention, it is possible to prepare a composition in which the volume change rate of a cured product after a certain period of time is close to 0, for example, by adjusting the optimum mixing amount of the resin component, the cement component, the radical polymerization initiator, the swelling material, and the like.

Claims (8)

1. A radically polymerizable resin composition characterized by comprising a radically polymerizable compound (A), an expandable material (B), a radical polymerization initiator (C) and an aggregate (D),
the aggregate (D) comprises cement,
the aggregate (D) is 330 to 800 parts by mass per 100 parts by mass of the radically polymerizable compound (A).
2. The radical polymerizable resin composition according to claim 1, wherein the radical polymerizable compound (a) comprises a vinyl ester resin and a radical polymerizable unsaturated monomer.
3. The radical polymerizable resin composition according to claim 1 or 2, wherein the swelling material (B) contains at least 1 material selected from the group consisting of quicklime and calcium sulfoaluminate.
4. The radical polymerizable resin composition according to any one of claims 1 to 3, wherein the radical polymerization initiator (C) is a hydroperoxide.
5. The radically polymerizable resin composition according to any one of claims 1 to 4, further comprising a metal-containing compound (E) and a thiol compound (F).
6. The radically polymerizable resin composition according to any one of claims 1 to 5, wherein the amount of the expanding material (B) is 0.3 to 30 parts by mass per 100 parts by mass of the radically polymerizable compound (A).
7. The radically polymerizable resin composition according to any one of claims 1 to 6, wherein the radical polymerization initiator (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A).
8. A cured product of the radical polymerizable resin composition according to any one of claims 1 to 7.
CN202080089185.1A 2019-12-26 2020-12-21 Radical polymerizable resin composition and cured product thereof Pending CN114846032A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019-235911 2019-12-26
JP2019235911 2019-12-26
PCT/JP2020/047644 WO2021132140A1 (en) 2019-12-26 2020-12-21 Radically polymerizable resin composition and cured product of same

Publications (1)

Publication Number Publication Date
CN114846032A true CN114846032A (en) 2022-08-02

Family

ID=76574758

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080089185.1A Pending CN114846032A (en) 2019-12-26 2020-12-21 Radical polymerizable resin composition and cured product thereof

Country Status (5)

Country Link
US (1) US20230058675A1 (en)
JP (1) JPWO2021132140A1 (en)
CN (1) CN114846032A (en)
TW (1) TWI767474B (en)
WO (1) WO2021132140A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0524898A (en) * 1991-07-18 1993-02-02 Toray Ind Inc Production of fiber-reinforced inorganic form
DE102004011388A1 (en) * 2004-03-05 2005-09-15 Röhm GmbH & Co. KG Methacrylate-based reaction resin, useful for repairing water conduits, containing inorganic material, preferably calcium oxide, to eliminate shrinkage and provide good wet adhesion
CN106420366A (en) * 2016-08-31 2017-02-22 哈尔滨工业大学 Ultralow-shrinkage composite resin and preparation method thereof
WO2019021560A1 (en) * 2017-07-27 2019-01-31 昭和電工株式会社 Method for coating surface of structure
JP2019026789A (en) * 2017-08-02 2019-02-21 旭化成株式会社 Binder for building structure
CN109653523A (en) * 2017-10-12 2019-04-19 蒲连影 A kind of civil buildings exterior wall crack repairing method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010002123A1 (en) * 2010-01-26 2011-07-28 Evonik Röhm GmbH, 64293 Formulations for the production of road markings with adhesion on dry and moist soil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0524898A (en) * 1991-07-18 1993-02-02 Toray Ind Inc Production of fiber-reinforced inorganic form
DE102004011388A1 (en) * 2004-03-05 2005-09-15 Röhm GmbH & Co. KG Methacrylate-based reaction resin, useful for repairing water conduits, containing inorganic material, preferably calcium oxide, to eliminate shrinkage and provide good wet adhesion
CN106420366A (en) * 2016-08-31 2017-02-22 哈尔滨工业大学 Ultralow-shrinkage composite resin and preparation method thereof
WO2019021560A1 (en) * 2017-07-27 2019-01-31 昭和電工株式会社 Method for coating surface of structure
JP2019026789A (en) * 2017-08-02 2019-02-21 旭化成株式会社 Binder for building structure
CN109653523A (en) * 2017-10-12 2019-04-19 蒲连影 A kind of civil buildings exterior wall crack repairing method

Also Published As

Publication number Publication date
WO2021132140A1 (en) 2021-07-01
JPWO2021132140A1 (en) 2021-07-01
TW202138408A (en) 2021-10-16
US20230058675A1 (en) 2023-02-23
TWI767474B (en) 2022-06-11

Similar Documents

Publication Publication Date Title
JP6690638B2 (en) Radical-polymerizable water-containing resin composition, method for curing the same, and method for producing radical-polymerizable water-containing resin composition
CN109863179B (en) Radical polymerizable resin composition
TWI754078B (en) Radical polymerizable resin composition and structural repair material
JP2016029125A (en) Two-pack curable resin composition, covering material, covering method and covering structure
JP6372922B2 (en) Resin composition, coating method using the same, and coating structure coated by the method
JP2011231231A (en) Radically curable unsaturated resin composition and coating material
JP2008106169A (en) Curable resin composition
CN114829432A (en) Radical polymerizable resin composition and cured product thereof
JP4147468B2 (en) Resin composition
CN114846032A (en) Radical polymerizable resin composition and cured product thereof
JP5131156B2 (en) Radical polymerizable resin composition
JP2008056823A (en) Radically polymerizable unsaturated resin composition, and molded article using the same
JP2003268054A (en) Free radical curing resin composition and civil engineering building material using the same
JP2006282767A (en) Unsaturated polyester resin composition and cured product thereof
JP7439991B2 (en) Recess filling material kit, its cured product, and recess filling method
WO2022224989A1 (en) Recess filling material kit, cured product thereof, and method for filling recess
JP4392591B2 (en) Cast molding resin composition and cast molding product
JP2005015642A (en) Radically polymerizable resin composition
JP2007084601A (en) Covering resin composition
JP4895471B2 (en) Resin composition for adhesive, adhesive and application thereof
JP2018072082A (en) Method for processing radioactive contaminated water
JP2007084701A (en) Room temperature curing unsaturated resin composition
JP2004338209A (en) Laminated molded body and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: Tokyo, Japan

Applicant after: Lishennoco Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: Showa electrical materials Co.,Ltd.

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230512

Address after: Tokyo, Japan

Applicant after: Showa electrical materials Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: SHOWA DENKO Kabushiki Kaisha